Reaction product of alkyl or alkenyl succinic anhydrides with benzotriazole or methyl benzotriazole

ABSTRACT

Hydrocarbon lubricant compositions are provided containing a minor proportion of the reaction product of at least one member of the group consisting of alkyl and alkenylsuccinic anhydrides and at least one member of the group consisting of benzotriazole and substituted benzotriazoles in a mole ratio of 1:1 to 1:2.

United States Patent [191 Andress, Jr.

a [451 May 20, 1975 REACTION PRODUCT OF ALKYL OR ALKENYL SUCClNlCANHYDRIDES WITH BENZOTRIAZOLE OR METHYL BENZOTRIAZOLE Related U.S.Application Data [60] Division of Ser. No. 247,067, April 24, 1972, Pat.No. 3,788,993, which is a continuation-in-part of Ser.

No. 222,642, Feb. 1, 1972, abandoned.

[52] U.S. Cl 260/308 B [51] Int. Cl. C07d 55/04; C07d 99/04 [58] Fieldof Search, 260/308 B, 326.5 F, 326.5 FM

[56] References Cited UNITED STATES PATENTS 3,784,645 1/1974 Chafetz eta1. 260/326.5 F 2/1973 Kahn et a1. 260/326.5 F

Primary Examiner-Alton D. Rollins Attorney, Agent, or Firm-Charles A.Huggett; Raymond W. Barclay; Benjamin 1. Kaufman [57] ABSTRACTHydrocarbon lubricant compositions are provided containing a minorproportion of the reaction product of at least one member of the groupconsisting of alkyl and alkenylsuccinic anhydrides and at least onemember of the group consisting of benzotriazole and substitutedbenzotriazoles in a mole ratio of 1:1 to 1:2.

. 5 Claims, No Drawings REACTION PRODUCT OF ALKYL OR ALKENYL SUCCINICANHYDRIDES WITH BENZOTRIAZOLE OR METHYL BENZOTRIAZOLE CROSS-REFERENCE TORELATED APPLICATIONS This is a division of application Ser. No. 247,067,filed Apr. 24, 1972 now US. Pat. No. 3,788,993, issued Jan. 29, 1974,which was a continuation-in-part of application Ser. No. 222,642, filedFeb. I, 1972, and now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to improved lubricant compositions and, in one of its aspects,relates more particularly to lubricant compositions that are normallysusceptible of causing deterioration of metal surfaces with which theymay come into contact or tend to undergo deterioration under conditionsof use. Still more particularly, in this aspect, the invention relatesto hydrocarbon lubricant compositions in the form of lubricating oilsand greases which normally exhibit the aforementioned shortcomings inperforming their intended functions.

2. Description of the Prior Art It is well known that certain types oflubricants, including hydrocarbon lubricating oils and greases, aresusceptible of causing deterioration, by oxidation or corrosion, whencoming into contact with various metal surfaces, for example in causingcopper-staining. In addition, such lubricants may also tend to undergodeterioration in performing their intended functions, for example in theimpairment of load-carrying characteristics, thus clearly indicating thenecessity for incorporating in such lubricants effective anti-oxidative,corrosion inhibiting and load-carrying improving agents.

SUMMARY OF THE INVENTION It has now been found that the aforementionedoxidative and corrosion inhibiting properties and, also, load-carryingcharacteristics of hydrocarbon lubricants can be effectively improved byincorporating, in minor proportion, sufficient to inhibit suchdeterioration, the reaction product of at least one member of the groupconsisting of alkyl and alkenylsuccinic anhydrides and at least onemember of the group consisting of benzotriazole and substitutedbenzotriazoles in a mole ratio of 1:1 to 1:2. For most applications,these reaction products are employed in an amount of from about .001 toabout 5%, and preferably in an amount of from about .01 to about I% byweight of the total lubricating composition.

Where the hydrocarbon lubricant comprises an oil of lubricatingviscosity, the lubricant may comprise many mineral or synthetic oils oflubricating viscosity. In in stances where high temperature stability isnot a prime requirement, mineral oil at a viscosity of at least 40 SSU.at 100F. and particularly those falling within'the range from about 60SSU. to about 6,000 SSU. at 100F. is preferably employed. In instanceswhere the lubricant comprises a synthetic hydrocarbon oil rather than amineral oil, or in combination therewith, various compounds of this typemay be successfully utilized. Typical synthetic vehicles include:polypropylene, polypropylene glycol, trimethylol propane esters,neopentyl and pentaerythritol esters, di-(2-ethy] hexyl) sebacate,di-2(ethyl hexyl) adipate, dibutyl phthalate, fluorocarbons, silicateesters, silanes, esters of phosphorous-containing acids, liquid ureas,ferrocene derivatives, hydrogenated mineral oils, chain-typepolyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituteddiphenyl ethers typified by a butylsubstituted bis(p-phenoxy phenyl)ether, phenoxy phenyl ethers, etc.

The aforementioned liquid hydrocarbon lubricants may also be employed incombination with a grease forming quantity of a thickening agent asvehicles in the production of greases containing the abovedescribedreaction product. For this purpose, a wide variety of materials may beemployed. These thickening or gelling agents may include any of theconventional metal salts or soaps, which are dispersed in thelubricating vehicle in grease-forming quantities, in such degree as toimpart to the resulting grease composition, the desired consistency.Other thickening agents that may be employed in the grease formation maycomprise the nonsoap thickeners, such as surface-modified clays andsilicas, aryl ureas, calcium complexes and similar materials. Ingeneral, grease thickeners may be employed which do not melt anddissolve when used at the required temperature within a particularenvironment; however, in all other respects, any material which isnormally employed for thickening or gelling hydrocarbon fluids forforming grease can be used in preparing the aforementioned improvedgrease in accordance with the present invention.

Any alkyl or alkenylsuccinic anhydride may be employed for reaction withbenzotriazole or substituted benzotriazoles in producing theaforementioned reaction product and incorporation in the hydrocarbonlubricant composition. Typically representative of such alkyl andalkenylsuccinic anhydrides are octenylsuccinic anhydride,dodecenylsuccinic anhydride, polybutenylsuccinic anhydride,hexadecenylsuccinic anhydride, eicosenylsuccinic anhydride,triacontenylsuccinic anhydride and isooctadecylsuccinic anhydride.Typically representative of the substituted benzotriazoles is tolyltriazole.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following data and examples willserve to illustrate the preparation of the aforementioned reactionproduct of an alkenylsuccinic anhydride and benzotriazole of the presentinvention, and to demonstrate the effectiveness of these reactionproducts in hydrocarbon lubricant compositions which are normallysusceptible of causing oxidative and corrosive deterioration of metalsurfaces with which they may come into contact or tend to undergodeterioration under conditions of use, and particularly with respect tothe use of these reaction products in hydrocarbon lubricating oils andgreases. It will be understood, of course, that it is not intended theinvention be limited to the particular compositions disclosed or to theoperations or manipulations involved. Various modifications thereof canbe employed and will be readily apparent to those-skilled in the art.

EXAMPLE 1 A mixture of 266 grams 1 mole) of distilled dodecenylsuccinicanhydride and 119 grams (l mole) of benzotriazole' was stirred at atemperature of about C. for a period of about 3 hours to form a viscousfluid.

' EXAMPLE 2 A mixture of 250 grams (0.93 mole) of undistilleddodecenylsuccinic anhydride and 1 grams (0.93 mole) of benzotriazole wasstirred at a temperature of about 125C. for a period of about 7 hours toform the final product.

EXAMPLE 3 A mixture of 133 grams (0.5 mole) distilled dodecenylsuccinicanhydride and 119 grams (1.0 mole) of benzotriazole was stirred at atemperature of about 135C. for a period of about 10 hours to form thefinal product.

EXAMPLE 4 A mixture of 300 grams (0.3 mole) ofa polybutenylsuecinicanhydride and 35 grams (0.3 mole) of benzotriazole was stirred at atemperature of about 135C. for a period of about 12 hours and then atabout 145C. for a period of about 4 hours to form the final product.

EXAMPLE 5 A mixture of 352 grams (1.0 mole) of isooctadecylsuccinicanhydride and 1 19 grams 1.0 mole) of benzotriazole was stirred at atemperature of about 135140C. for a period of about 6 hours to form thefinal product.

EXAMPLE 6 lows:

ASLE-64-9 CORROSION TEST ASLE Slideway Lubricant Accelerated BreakdownTest 1. Test Procedure for Normal Test Conditions Place clean polishedpieces of copper and carbon steel rods (approximately 0.25 inchesdiameter by 3.0 inches long) in a 100 cc griffin beaker containing 35 to40 grams of oil sample. Put beaker and contents into an electric dryingoven for 24 hours, maintaining a temperature of 210 2F. (99 i 1C.). Testperiod may be extended 72 hours if necessary.

Test specimen pieces must be freshly polished and placed in pentane for30 minutes before using. These polished specimens must then be usedwithin 30 minutes after the original 30 minute pentane deactivationperiod.

Test results:

Condition of Steel Rod Condition of Copper rod Precipitate of SludgeEvaporation Loss Wt.

11. Wet ASLE-64-9 Place 50 grams of oil sample in a 4 g. bottle, add 0.5m1 of distilled water and stir vigorously for about 1 minute. Placeclean polished pieces of copper and carbon steel rods in the beaker.Stopper with a cork and place into an electric drying oven for 72 hours,maintaining a temperature of 210 i 2F. (99 i 1C.).

Test specimen pieces must be freshly polished and placed in pentane for30 minutes before using. These polished specimens must then be usedwithin 30 minutes after the original 30 minute pentane deactivationperiod.

Test results:

Condition of Steel Rod Condition of Copper Rod Precipitation of SludgeNote 1: For polishing the rods, medium emery cloth is used.

Note 2: Specimens should be rated as is when removed from the oil (Nowashing).

Note 3: Steel rods should be rated No Stain, Trace Stain," MediumStain," Heavy Stain." Copper rods should be given an ASTM D-130 ratingplus a verbal description such as No Stain," Light Brown Stain," MediumBrown Stain," Dark Brown Stain, Black Stain or Black Coating, etc. Theresults obtained employing the above-described ASLE-64-9 Corrosion Testare set forth in the following table:

ASLE64-9 Corrosion Test Conc., Steel Copper Sludge Base Oil 0 Lt. 4ALight Stain Example 1 0.1 Pass 1B Nil Example 2 0.1 Pass 18 Nil Example3 0.1 Pass 1A Nil Example 4 0.1 Pass 18 Nil Example 5 0.] Pass 1B NilExample 6 0.1 Pass 1A Nil ASTM Copper Strip Test D-6 3 Hr. at 250F.

Rating Base Oil 4A Example 1 1B Example 2 1B Example 3 1B Example 4 1BExample 5 1B Example 6 1B As will be seen from the foregoing table, thepresence of the reaction product of alkyl and alkenylsuccinic anhydridesand benzotriazole and substituted benzotriazoles result in a markedimprovement in inhibiting copper staining. 7

Another test was conducted in accordance with Federal Standard No. 7913,method 5308.6, for determining oxidation and corrosion resistance ofliquid hydro- Oxidation and Corrosion Test Federal Test Standard No.7918 Method 5308.6 Test run for 72 hours at 400F.

Cone, Copper Loss in Mg.

Base Oil 0 Base Oil Example I 0.]

As will be seen from the comparative data of the foregoing table, thepresence of the reaction product of the alkenylsuccinic anhydride andbenzotriazole results in a marked improvement in reducing copper loss byoxidation and corrosion.

Another test was conducted in accordance with the standard Timken O.1(.Load Test, for determining the effect of the reaction product ofalkenylsuccinic anhydrides and benzotriazole with regard toload-carrying characteristics of a base oil. In this test the base oilwas comprised of an SAE 30 grade mineral oil having an SUV at 210F. ofapproximately 69.1. The results obtained are shown in the followingtable:

Timken O.l(. Load Test Conc., Load pounds/sq.in.

Base Oil 0 50 Base Oil Example 1 0.1 70

sulted in a marked improvement in the load-carrying characteristics ofthe base oil.

From the foregoing examples and comparative data, it will be noted thatthe presence of the aforementioned reaction product of the reactionproduct of alkyl and alkenylsuccinic anhydrides and benzotriazole orsubstituted benzotriazoles are markedly effective in improving lubricantcompositions which are normally susceptible of causing oxidative andcorrosive deterioration of metals with which they may come into contactand tend to undergo deterioration under conditions of use. These liquidhydrocarbon lubricants thus treated. as hereinbefore indicated may beemployed as the lubricant vehicle in combination with known thickeningagents for providing improved greases, incorporating the benefits of theimproved base lubricant oil vehicle.

It will be understood that although the present invention has beendescribed with preferred embodiments, various modifications andadaptations may be resorted to without departing from the spirit of theinvention as those skilled in the art will readily understand.

I claim:

1. The reaction product of at least one member of the group consistingof alkyl and alkenylsuccinic anhydrides wherein the alkyl and alkenylgroups each contain from eight to 30 carbon atoms, and at least onemember of the group consisting of benzotriazole and methyl benzotriazolein a mole ratio of from 1:1 to 1:2 at a temperature from about C. toabout C.

2. The reaction product of claim 1 wherein the alkenylsuccinic anhydrideis octenylsuccinic anhydride.

3. The reaction product of claim 1 wherein the alkenylsuccinic anhydrideis a polybutenylsuccinic anhydride.

4. The reaction product of claim 1 wherein the alkenylsuccinic anhydrideis triacontenylsuccinic anhydride.

5. The reaction product of claim 1 wherein the alkylsuccinic anhydrideis isooctadecylsuccinic anhydride.

1. THE REACTION PRODUCT OF AT LEAST ONE MEMBER OF THE GROUP CONSISTINGOF ALKYL AND ALKENYLSUCCINIC ANHYDRIDES WHEREIN THE ALKYL AND ALKENYLGROUPS EACH CONTAIN FROM EITHT TO 30 CARBON ATOMS, AND AT LEAST ONEMEMBER OF THE GROUP CONSISTING OF BENZOTRIAZOLE AND METHYL BENZOTRIAZOLEIN A MOLE RATIO OF FROM 1:1 TO 1:2 AT A TEMPERATURE FROM ABOUT 125*C. TOABOUT 145*C.
 2. The reaction product of claim 1 wherein thealkenylsuccinic anhydride is octenylsuccinic anhydride.
 3. The reactionproduct of claim 1 wherein the alkenylsuccinic anhydride is apolybutenylsuccinic anhydride.
 4. The reaction product of claim 1wherein the alkenylsuccinic anhydride is triacontenylsuccinic anhydride.5. The reaction product of claim 1 wherein the alkylsuccinic anhydrideis isooctadecylsuccinic anhydride.